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Photocatalysts for steering charge transfer and radical reactions in biorefineries

Nature Synthesis volume 3, pages 438–451 (2024)Cite this article

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Abstract

Photocatalysis has emerged as a green protocol for biorefineries thanks to sustainable energy input. The unique radical mechanism of photocatalysis allows the decomposition of raw biomass and the precise functionalization of platform molecules, but radicals with open-shell electronic structures are highly active, resulting in diverse products. Control of the radical mechanism relies on photocatalysts guiding interfacial charge transfer for chemical bond breaking. The reaction behaviour of radicals and the surface states of semiconductor photocatalysts are therefore crucial for controlling the efficiency and selectivity of biorefineries. Here we discuss the factors that influence the interfacial charge transfer and radical reactions in photocatalytic biorefineries, including the surface structure and electronic states of semiconductors and the catalytic properties of cocatalysts. Recognition of these factors will feed back the expected structure of semiconductors and cocatalysts, assisting with the design of photocatalysts for the efficient and selective refining of native biomass.

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Fig. 1: Overview of the biomass involved in photocatalytic biorefineries.
Fig. 2: Overview of the reaction types involved in PBR.
Fig. 3: Strategies for engineering photocatalysts for boosted hole or electron transfer in PBR.
Fig. 4: Strategies for engineering photocatalysts for selectively extracting holes or electrons in PBR.
Fig. 5: Overview of ROR formation and the principle of controlling the reaction of CCRs.
Fig. 6: Strategies for engineering photocatalysts to control the generation of RORs in PBR.
Fig. 7: Strategies for engineering photocatalysts to control the reaction patterns of CCRs.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22025206, 22172157, 22202199 and 21991090), the Dalian Innovation Support Plan for High Level Talents (2022RG13), DICP (grant no. DICP I202326) and the Youth Innovation Promotion Association (YIPA) of the Chinese Academy of Sciences (2023192). We also acknowledge instrumental support from the Liaoning Key Laboratory of Biomass Conversion for Energy and Material. Y. Zou is acknowledged for drawing the Graphical Abstract.

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  1. These authors contributed equally: Zhuyan Gao, Puning Ren.

Authors and Affiliations

  1. State Key Laboratory of Catalysis, National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Zhuyan Gao, Puning Ren, Lulu Sun, Nengchao Luo & Feng Wang

  2. University of Chinese Academy of Sciences, Beijing, China

    Zhuyan Gao, Puning Ren & Feng Wang

Authors
  1. Zhuyan Gao
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  2. Puning Ren
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  3. Lulu Sun
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  4. Nengchao Luo
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  5. Feng Wang
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Contributions

F.W. and N.L. conceived the outline of this Review. Z.G., P.R. and N.L. composed the figures, and wrote and revised the manuscript. L.S. collected and organized the references.

Corresponding authors

Correspondence to Nengchao Luo or Feng Wang.

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Nature Synthesis thanks Ridha Djellabi and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Gao, Z., Ren, P., Sun, L. et al. Photocatalysts for steering charge transfer and radical reactions in biorefineries. Nat. Synth 3, 438–451 (2024). https://doi.org/10.1038/s44160-024-00499-4

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